EP1030871A1 - Verfahren zur herstellung einer zweischichtigen lackierung und für dieses verfahren geeignete lacke - Google Patents
Verfahren zur herstellung einer zweischichtigen lackierung und für dieses verfahren geeignete lackeInfo
- Publication number
- EP1030871A1 EP1030871A1 EP98961107A EP98961107A EP1030871A1 EP 1030871 A1 EP1030871 A1 EP 1030871A1 EP 98961107 A EP98961107 A EP 98961107A EP 98961107 A EP98961107 A EP 98961107A EP 1030871 A1 EP1030871 A1 EP 1030871A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- malonic acid
- dialkyl
- isocyanate groups
- blocked
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 210000003298 dental enamel Anatomy 0.000 title abstract description 5
- 238000000576 coating method Methods 0.000 title description 11
- 239000011248 coating agent Substances 0.000 title description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 61
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 53
- -1 cycloaliphatic Chemical group 0.000 claims abstract description 48
- 150000002148 esters Chemical class 0.000 claims abstract description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 36
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 239000004922 lacquer Substances 0.000 claims description 33
- 239000003973 paint Substances 0.000 claims description 31
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 150000002690 malonic acid derivatives Chemical class 0.000 claims description 14
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 150000001298 alcohols Chemical class 0.000 claims description 11
- 239000004971 Cross linker Substances 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical class CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 8
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical class CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002966 varnish Substances 0.000 claims description 5
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical class CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 4
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical class CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 claims description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical group CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 24
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- 239000002253 acid Substances 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 13
- 239000000178 monomer Substances 0.000 description 12
- 239000002981 blocking agent Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- 229920000180 alkyd Polymers 0.000 description 8
- 150000003333 secondary alcohols Chemical class 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 229920000058 polyacrylate Polymers 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000004383 yellowing Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 229920003180 amino resin Polymers 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
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- 239000008199 coating composition Substances 0.000 description 5
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- 239000003960 organic solvent Substances 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 4
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- 239000000945 filler Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
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- 239000004033 plastic Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- GUSLDHIGLVOREE-UHFFFAOYSA-M sodium;4-dodecylphenolate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C([O-])C=C1 GUSLDHIGLVOREE-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical class CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical class CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical class CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical class CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical class CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical class CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical class CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical class [H]C([*])=C([H])[H] 0.000 description 1
- 239000004924 water-based lacquer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8093—Compounds containing active methylene groups
Definitions
- the present invention relates to paints containing
- the present invention also relates to the production and use of the lacquers and the production of the blocked polyisocyanates used in the lacquers according to the invention and their use in topcoats and clearcoats.
- coating compositions are known from DE-C-195 29 124, in which it is essential to the invention that a mixture of a styrene-containing and a styrene-free acrylate copolymer is used as the binder.
- These coating compositions contain one or more free or blocked polyisocyanates as crosslinking agents.
- other blocking agents in DE-C-195 29 124 also called dialkyl malonate, such as diethyl malonate, diisopropyl and di-tert. -butyl ester, of which malonate dialkyl esters diethyl malonate is preferably used.
- Coating compositions are also known from ÜS-A-4, 677, 180 which, in addition to a hydroxy-functional binder, contain blocked isocyanates in which the isocyanate groups are blocked with C1- to C12-alkylmalonates.
- ÜS-A-4, 677, 180 which, in addition to a hydroxy-functional binder, contain blocked isocyanates in which the isocyanate groups are blocked with C1- to C12-alkylmalonates.
- diethyl malonate is mentioned as an example of suitable malonates.
- Another disadvantage is that these coating compositions known from US Pat. No. 4,677,180 absolutely require the addition of a low molecular weight compound with at least 2 OH groups per molecule as stabilizing agent.
- JP-A-2-242867 describes a basecoat / clearcoat process in which powerful aqueous transparent topcoats are applied which (A) contain a synthetic resin containing hydroxyl groups, (B) an aminoplast resin and (C) a blocked polyisocyanate Contain, the components (B) and (C) are to be selected so that the temperature at which a chemical reaction starts between (A) and (C) is at most 20 ° C below and at most 50 ° C above the temperature at which starts a chemical reaction between (A) and (B).
- Aliphatic monoalcohols, oximes and caprolactams are preferably used as blocking agents for the production of component (C).
- malonic acid esters are also mentioned as suitable blocking agents.
- the transparent topcoats described in JP-A-2-242 867 provide coatings which are particularly useful in terms of resistance to organic Solvents and acids, gloss, transparency and resistance to yellowing should be improved.
- DE-A-23 42 603 describes a process for the preparation of polyisocyanates which are blocked with malonic acid dialkyl esters having 1 to 4 carbon atoms in the alcohol radical, and the use of the blocked isocyanates in paints. Further details on the composition of the paints and their use are, however, not contained in DE-A-23 42 603.
- the present invention is therefore based on the object of providing lacquers in which both the finished one-component lacquer and the crosslinker used have sufficient storage stability and which can simultaneously be cured at the lowest possible temperatures. This means that when the finished one-component lacquer is stored for 6 months at room temperature, there is an increase in viscosity of less than 10% or that there is no significant increase in viscosity when the crosslinker is stored for longer periods of up to 2 years or more.
- the lacquers should only guarantee a low tendency to yellowing when baked, as well as good acid resistance, scratch resistance and a high gloss of the resulting coatings.
- the lacquers should be suitable for the production of multi-layer lacquers and in particular should meet the requirements usually placed in the field of automotive serial lacquering.
- lacquers of the type mentioned at the outset which are characterized in that the isocyanate groups are capped component (B) from a mixture of malonic acid dialkyl esters
- R ** -, R 2 and R 3 each have the same or different aliphatic and / or cycloaliphatic and / or araliphatic secondary alkyl radicals with at least 3 carbon atoms and
- R 4 represents an aliphatic, cycloaliphatic, aromatic or araliphatic hydrocarbon radical
- the present invention also relates to the production and use of the lacquers and to the production of the blocked polyisocyanates used in the lacquers according to the invention and their use in topcoats and clearcoats.
- the lacquers according to the invention can be hardened at low stoving temperatures to give coatings with good acid resistance and scratch resistance.
- the blocked polyisocyanates used according to the invention can be produced simply and inexpensively.
- the paints according to the invention are suitable for the production of multi-layer paints, meet the requirements usually placed in the field of automotive serial painting and can also be processed well with a low content (e.g. less than 50% by weight) of organic solvents.
- any hydroxyl-containing synthetic resin suitable for transparent topcoats can be used as component (A) or a mixture of such synthetic resins can be used.
- the resins are preferably selected so that component (A) has an OH number of 40 to 240 mgKOH / g, particularly preferably of 60 to 150 mgKOH / g.
- component (A) it is preferred to use hydroxyl group-containing polyester resins and / or hydroxyl group-containing alkyd resins and / or hydroxyl group-containing polyacrylate resins and mixtures of these resins.
- the synthetic resins used as component (A) generally have number average molecular weights of 1,500 to 30,000, preferably 2,000 to 15,000, particularly preferably 2,500 to 7,500.
- Hydroxyl group-containing polyester resins, alkyd resins and polyacrylate resins are well known. Examples of such resins and their preparation are described, for example, in JP-A-2-24 28 67, DE-B-26 39 491, EP-A-403 044, US-A-3,639,147, DE-A-33 33 072, DE-A-38 14 853, GB-A-2 012 191, US-A-3,953,644, EP-A-260 447, DE-A-39 03 804, EP-A-320 552, DE-A-36 28 124, US-A-, 719, 132, EP-A-
- As component (A) are also those mentioned in the European patent application EP-A-767 185 and those in the US patents US-A-5,480,943, US-A-5,475,073 and US-A-5, 53, 598 functional Suitable connections.
- component (A) it is particularly preferred to use polyacrylate resins which can be prepared by
- polyacrylate resins with hydroxyl numbers from 40 to 240, preferably 60 to 150, acid numbers from 0 to 35, preferably from 5 to 20, glass transition temperatures from -35 to + 70 ° C, preferably from -20 to + 40 ° C and number average molecular weights of 1,500 up to 30,000, preferably from 2,000 to 15,000, (determined by gel permeation chromatography using a polystyrene standard).
- Examples of (a) components are: methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl and 2-ethylhexyl acrylate or methacrylate and cyclohexyl acrylate, cyclohexyl methacrylate, tert. -Butylcyclohexyl acrylate, tert. -Butylcyclohexyl methacrylate, isobornyl acrylate and isobornyl methacrylate.
- Examples of (b) components are: hydroxyethyl, hydroxypropyl and hydroxybutyl acrylate or methacrylate.
- Examples of (d) components are: vinylaromatics, such as, for example, styrene, vinyltoluene, ⁇ -methylstyrene, -ethylstyrene, nucleus-substituted diethylstyrenes, isopropylstyrene, butylstyrenes and methoxystyrenes; Vinyl ethers, such as, for example, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether and vinyl esters, such as, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and the vinyl ester of saturated, aliphatic monocarboxylic acids having 9 to 11 carbon atoms
- the person skilled in the art can easily control the hydroxyl number and the acid number of the polyacrylate resins by the amount of component (b) or (c) used.
- the glass transition temperature of the polyacrylate resins is determined by the type and amount of the monomers used. The selection of the monomers can be carried out by a person skilled in the art with the aid of the following formula, with which the glass transition temperatures of polyacrylate resins can be approximately calculated:
- TQ glass transition temperature of the polyacrylate resin x number of different monomers polymerized into the polyacrylate resin
- W n weight fraction of the nth monomer
- Gn glass transition temperature of the homopolymer from the nth monomer
- polyester resins or alkyd resins which can be prepared by
- component () hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, endomethylene tetrahydrophthalic acid, malonic acid, succinic acid acid, glutaric acid, adipic acid, pimeline acid, cork acid, azelaic acid and sebacic acid.
- aromatic polycarboxylic acids such as e.g. Phthalic acid, isophthalic acid, terephthalic acid, halophthalic acids, such as tetrachloro- or tetrabromophthalic acid, trimellitic acid, pyro-ellitic acid and others. be used.
- component ( ⁇ ) examples are: pentaerythritol, trimethylolpropane, trimethylolethane and glycerin.
- component ( ⁇ ) examples are:
- Ethylene glycol diethylene glycol, propylene glycol, neopentyl glycol, 2-methyl-2-propylpropanediol-1, 3, 2-ethyl-2-butylpropanediol-1, 3, 2,2, -trimethylpentanediol-1, 5, 2,2, 5 -Tr ⁇ methylhexandiol-1, 6, Hydroxypivalinsaurene-pentylglykolester and Dimethylolcyclohexan.
- component ( ⁇ ) examples include 2-ethylhexanoic acid, lauric acid, isooctanoic acid, isononanoic acid and monocarboxylic acid mixtures which are obtained from coconut oil or palm kernel oil.
- the lacquers contain, as crosslinking component (B), one or more di- and / or polyisocyanates in which a mixture of malonic acid dialkyl esters, consisting of, is used to mask the isocyanate groups
- R ⁇ , R 2 and R 3 each the same or different aliphatic and / or cycloaliphatic and / or araliphatic secondary alkyl radicals having at least 3 carbon atoms and
- R 4 represents an aliphatic, cycloaliphatic, aromatic or araliphatic hydrocarbon radical
- b2) 70 to 15% by weight, preferably 50 to 30% by weight, of one or more dialkyl malonates different from component (b1), the sum of the parts by weight of components (bl) and (b2) being 100% by weight.
- Preferred components (b1) are dialkyl malonates of the formula (I).
- R - * - 'R 2 and R 3 are preferably secondary alkyl radicals having 3 to 18 carbon atoms and particularly preferably having a maximum of 8 carbon atoms.
- the radical R 4 preferably has 1 to a maximum of 18 carbon atoms, particularly preferably 1 up to 10 carbon atoms.
- Blocking agents (b1) of the formulas (I) and (II) used according to the invention are esters of malonic acid with aliphatic and / or cycloaliphatic and / or aromatic secondary alcohols, in particular esters of malonic acid with 2-propanol, 2-butanols, such as e.g. 2-butanol, 3, 3-dimethylbutanol-2, 2-pentanols, such as e.g. Esters with 3-methylpentanol-2, 4-methylpentanol-2, 3-pentanols, e.g.
- Mixed esters of malonic acid can also be used as blocking agents.
- the malonic acid dialkyl esters of secondary alcohols are preferably the malonic acid esters of isopropanol, 2-butanols, 2-pentanols and 3-pentanols, very particularly preferably 2-propanol, 2-butanol, 2-pentanol and 3-pentanol.
- the dialkyl malonates of secondary alcohols are used together with one or more other dialkyl malonates (b2).
- these other malonic acid dialkyl esters (b2) are esters of malonic acid with tertiary alcohols, but in particular with primary alcohols, such as, for example, methanol, ethanol, n-propanol, n-butanols, isobutanols, n-pentanols, iso-pentanols, n- Hexanols, iso-hexanols, 2-ethylhexanol, isononanols, isodecanols, isotricyl alcohols, fatty alcohols, benzyl alcohol and others.
- Mixed esters of malonic acid can in turn also be used as blocking agents (b2).
- a mixture of bl) malonic acid ester (s) of isopropanol, 2-butanols, 2-pentanols and / or 3-pentanols and b2) dimethylmalonate and / or diethylmalonate is particularly preferably used.
- a mixture of b1) diisopropyl malonate and / or di-sec is very particularly preferred. butyl malonate and b2) dimethyl malonate and / or diethyl malonate.
- polyisocyanates that can be used in the coating field can be used to produce component (B).
- polyisocyanates whose isocyanate groups are bonded to aliphatic or cycloaliphatic radicals.
- examples of such polyisocyanates are hexamethylene diisocyanate, isophorone diisocyanate, methylamine hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and 1,3-bis (2-isocyanate propyl-2-) benzene (TMXDI) and mixtures thereof or oligomers derived from these isocyanates.
- the oligomers of these polyisocyanates include, for example, adducts with polyols, in particular low molecular weight polyols, such as trimethylolpropane, or polyester polyols and / or Polyether polyols, and isocyanurate group and / or biuret group and / or allophanate group and / or uretdione group-containing and / or carbodumide-containing polyisocyanates or mixtures of such compounds derived from these polyisocyanates are considered.
- polyols in particular low molecular weight polyols, such as trimethylolpropane, or polyester polyols and / or Polyether polyols
- isocyanurate group and / or biuret group and / or allophanate group and / or uretdione group-containing and / or carbodumide-containing polyisocyanates or mixtures of such compounds derived from these polyisocyanates are considered.
- Particularly preferred polyisocyanates are hexamethylene diisocyanate and / or isophorone diisocyanate, polyisocyanates containing isocyanurate or biuret groups derived from these diisocyanates, which preferably contain more than two isocyanate groups in the molecule, and reaction products of hexamethylene diisocyanate and isophorone diisocyanate or a mixture of hexamethylene diisocyanate and isophorone diisocyanate and isocyanate diisocyanate and 0.5 equivalents of a low molecular weight polyol with a molecular weight of 62 to 500, preferably from 104 to 204, in particular a toluene, such as trimethylol propane, are used.
- Component (B) can be prepared, for example, by adding a polyisocyanate or a mixture of polyisocyanates in a manner known per se to the mixture of one or more malonic acid esters (b1) and one or more different malonic acid dialkyl esters (b2) is implemented. It is only essential that the amounts of the individual malonic acid dialkyl esters are chosen such that 30 to 85% by weight, preferably 50 to 70% by weight, of the malonic acid dialkyl ester used for capping the isocyanate groups of component (B) or more dialkyl malonates of the formulas (I) and / or (II).
- the polyisocyanate or the mixture of the polyisocyanates is reacted in a known manner at temperatures which are generally between 50 and 130.degree.
- This implementation can be done in non-protic solvents such as for example aromatic hydrocarbons, esters, ketones, glycol ether esters, aliphatic and / or cycloaliphatic hydrocarbons.
- the reaction is usually carried out in the presence of basic catalysts, such as, for example, alkali metal alcoholates, alkali metal phenolates or alkali metal salts of alkane carboxylic acids or their derivatives, preferably sodium salts of the compounds mentioned.
- the polyisocyanate or the mixture of polyisocyanates can be reacted with the malonates until the desired NCO equivalent weight is reached.
- the reaction can be continued until isocyanate groups can no longer be detected. In practice, this can involve the use of very large surpluses
- paints with the good properties described above are obtained even if at least 50%, preferably at least 90%, of the isocyanate groups of the polyisocyanate or the mixture of polyisocyanates are reacted with the malonates and the remaining isocyanate groups are reacted with a hydroxyl - Group-containing compound or a mixture of compounds containing hydroxyl groups are implemented.
- Low-molecular-weight aliphatic or cycloaliphatic polyols such as neopentyl glycol, dimethylolcyclo-hexane, ethylene glycol, diethylene glycol, propylene glycol, 2-methyl-2-propyl-propanediol-1, 3, 2-ethyl-2-butyl-propanediol-1, are preferably used as hydroxyl-containing compounds. 3, 2, 2, 4-trimethylpentanediol-1, 5 and 2,2,5-trimethylhexanediol-1, 6 or the hydroxyl-containing synthetic resins which can be used as component (A).
- Component (B) can also be obtained by mixing polyisocyanates blocked with various malonic esters in such a ratio that a mixture is obtained in which the above-mentioned ratio of malonic esters with secondary alcohols is ensured. This procedure for the preparation of component (B) is less preferred.
- Polyisocyanates are particularly easy to produce by
- the isocyanate groups of the di- and / or polyisocyanate are at least partially reacted with dimethyl malonate and / or diethyl malonate,
- reaction product obtained in stage (1) is reacted with a compound containing hydroxyl groups or a mixture of compounds containing hydroxyl groups and
- reaction product obtained in stage (1) or (2) is reacted with an aliphatic and / or cycloaliphatic and / or aromatic alcohol having at least 3 carbon atoms, preferably secondary alcohols, or a mixture of such alcohols .
- This process is preferably used for the preparation of the malonic acid dialkyl esters of the formulas (I) and (II) and the blocked isocyanates prepared by this process are preferably used as component (B) in the paints according to the invention.
- Stage (1) of the process is known and is described, for example, in DE-A-42 04 518.
- the Reaction conditions correspond to the conditions given above for the reaction with the malonic esters of secondary alcohols.
- step (1) of the process the isocyanate groups of the di- and / or poly-isocyanate are only partially reacted with dimethyl malonate and / or diethyl malonate, i.e. that the reaction product obtained in stage (1) still has free isocyanate groups.
- This reaction product with free isocyanate groups obtained in step (1) can then be reacted in a particularly preferred process with a compound containing hydroxyl groups or with a mixture of compounds containing hydroxyl groups (step (2) of the process).
- a compound containing hydroxyl groups or with a mixture of compounds containing hydroxyl groups (step (2) of the process).
- Low molecular weight aliphatic or cycloaliphatic polyols, polyester polyols and / or polyether polyols are preferably used as compounds containing hydroxyl groups. Examples of suitable ones
- a stage (1) can also be based on a dusocyanate and the oligomerization to a urethane or the like. after partial capping (stage (1)) in this stage (2).
- stage (3) of the process with the desired alcohol (aliphatic and / or cycloaliphatic and / or aromatic alcohol with more than 2 carbon atoms or a mixture of such alcohols) secondary alcohol) implemented.
- This reaction usually takes place at temperatures between 80 and 150 ° C., preferably between 110 and 130 ° C. That at methanol and / or ethanol released from this transesterification is generally distilled off. If the reaction product used in stage (3) still has free isocyanate groups, urethanization is of course also carried out in addition to the transesterification.
- this urethanization proceeds faster than the transesterification. It has also been found that, in general, re-urethanization with elimination of the malonic ester only takes place to a limited extent. It is also possible to carry out the transesterification reaction in such a way that only parts of the original dimethyl malonate or diethyl malonate are transesterified.
- Components (A) and (B) are preferably used in the varnishes according to the invention in amounts such that the equivalent ratio of the hydroxyl groups of component (A) to the isocyanate groups of component (B) is between 1.6: 1 and 0.7: 1, preferably between 1.3: 1 and 0.9: 1.
- lacquers according to the invention can optionally also contain one or more further crosslinking agents, for example amino resins or polyisocyanates blocked with other capping agents, as component (C).
- further crosslinking agents for example amino resins or polyisocyanates blocked with other capping agents, as component (C).
- any, in particular any, aminoplast resin suitable for transparent topcoats or a mixture of such aminoplast resins can be used as component (C).
- Aminoplast resins are condensation products made from aldehydes, in particular formaldehyde and, for example, urea,
- the aminoplast resins contain alcohol, preferably methylol groups, which are generally partially or preferably completely etherified with alcohols.
- Melamine-formaldehyde resins etherified with lower alcohols, in particular with methanol or butanol, are preferably used as component (C).
- cross-linking components based on T ⁇ azm can be used with the hydroxyl groups of the binder with the formation of esters.
- the triazm-based crosslinkers which react with the hydroxyl groups of the binder to form ester groups are transesterification crosslinkers, such as tris (alkoxycarbonylammo) triazm or the like, as described, for example, in EP-A-604 922.
- component (C) is usually used in an amount of 3 to 30% by weight, preferably 10 to 15% by weight, based on the weight of the binder. If the paints contain component (C), the amount of crosslinking agent (B) used is reduced accordingly, i.e. l.a reduced by about half the amount.
- the paints according to the invention can be formulated as aqueous, but in particular as solvent-containing, liquid paints. If the lacquers are formulated as aqueous lacquers, the usual methods are used in order to be able to stably distribute the blocked polyisocyanates in the aqueous phase. This can be done in the Those skilled in the art are, for example, using a carrier resin, the use of emulsifiers or by incorporating hydrophilic groups, such as acid groups.
- the non-aqueous paints contain the usual amounts of organic solvents which are customary for the production of paints.
- the glass transition temperature of the capped polyisocyanates and the glass transition temperature of component (A) is sufficiently high (generally higher than 80 ° C.) - the lacquers according to the invention as powder lacquers or as powder slurries (aqueous dis formulations of systems initially produced as solid mixtures).
- the paints according to the invention can also contain other additives that are used for the respective formulation, such as e.g. Stabilizers such as light stabilizers, antioxidants and free radical scavengers, flow control agents, rheology additives, trickling aids, etc., preferably in an amount of 0.2 to 5.0 wt .-%, based on the total weight of the paint.
- Stabilizers such as light stabilizers, antioxidants and free radical scavengers
- flow control agents such as light stabilizers, antioxidants and free radical scavengers
- rheology additives such as sodium bicarbonate
- trickling aids preferably in an amount of 0.2 to 5.0 wt .-%, based on the total weight of the paint.
- the lacquers according to the invention can optionally also contain customary pigments and / or fillers.
- the amount of pigments and / or fillers used is generally chosen so that the coloring required in layer thicknesses of 25 to 50 ⁇ m is achieved. The amount is therefore generally 0.9 to 30 wt .-%, based on the total weight of the paint. If they are used as transparent top coats, they contain no or only transparent pigments.
- the lacquers according to the invention are also suitable for the production of multi-layer lacquers. They can be used as basecoats and preferably as clearcoats. The present invention therefore also relates to a method for producing a multilayer coating, in which
- the basecoat and / or the topcoat are a paint according to the invention.
- step (I) of the process according to the invention in addition to the paints according to the invention, in principle all pigmented basecoats suitable for producing two-coat paints can be used.
- basecoats are well known to those skilled in the art. Both water-dilutable basecoats and basecoats based on organic solvents can be used.
- Suitable basecoats are described for example in US-A-3, 639, 147, DE-A-33 33 072, DE-A-38 14 853, GB-A-2 012 191, US-A-3, 953, 644 , EP-A-260 447, DE-A-39 03 804, EP-A-320 552, DE-A-36 28 124, US-A-4, 719, 132, EP-A-297 576, EP- A-69 936, EP-A-89 497, EP-A-195 931,
- EP-A-228 003, EP-A-38 127 and DE-A-28 18 100 EP-A-228 003, EP-A-38 127 and DE-A-28 18 100.
- EP-A-228 003, EP-A-38 127 and DE-A-28 18 100 EP-A-228 003, EP-A-38 127 and DE-A-28 18 100.
- EP-A-228 003, EP-A-38 127 and DE-A-28 18 100 can also be found for further information about the basecoat / clearcoat process in question.
- stage (2) of the process according to the invention the solvents or water are removed from the basecoat applied in stage (1) in an evaporation phase.
- the basecoat film can also be baked, but this is disadvantageous for economic reasons, because then two-coat painting 2 is required instead of a baking process.
- the transparent topcoat according to the invention is used.
- the two-coat lacquers produced with the topcoats used according to the invention also have the advantageous properties in particular if they are used under the stoving conditions currently used in automotive series painting (30 minutes at 110 ° C. to 10 minutes at 150 ° C., preferably 30 minutes at 130 ° C.) have been branded.
- the paints according to the invention can of course also be used for other paints. They can therefore also be applied to other substrates, such as metal, wood or paper.
- the application is carried out using conventional methods, for example spraying, knife coating, rolling, dipping or brushing.
- non-aqueous paints primed or non-primed plastics such.
- B ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PC, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP,
- PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP can be painted.
- the plastics to be painted can of course also be polymer blends, modified plastics or fiber-reinforced plastics. They can also be used for the coating of plastics typically used in vehicle construction, in particular motor vehicle construction. However, it is a prerequisite, of course, that the substrates tolerate the stoving temperatures of, for example, 90 ° C. for 45 minutes.
- non-functionalized and / or non-polar substrate surfaces these have to be subjected to a pretreatment, such as plasma or flame treatment, in a known manner before coating.
- Heating by means of an oil circulation thermostat, a blade stirrer with a Ruhr lock, a thermometer for checking the temperature of the reaction mixture, an inlet tube for a nitrogen blanket gas flow and a metering vessel for a monomer mixture and an initiator solution are 870 g of a commercially available solvent from a fraction of aromatic hydrocarbons with a boiling range of 158 Weighed ° C to 172 ° C at normal pressure. The solvent is heated to 140 ° C with stirring. Then the dosing for the
- Initiator solution a solution of 87 g tert. -Butylper-2- ethylhexanoate m 87 g of the aromatic solvent described above evenly metered the reactor within 0.75 h. 0.25 h after the start of the initiator addition, the metering vessel for the monomer mixture becomes a mixture of 291 g styrene, 367 g n-butyl acrylate, 364 g n-butyl methacrylate, 405 g 2-hydroxypropyl acrylate and 29.0 g acrylic acid within 4 h evenly metered into the reactor.
- the temperature is kept at 140 ° C.
- the reaction mixture is kept at 140 ° C.
- the degree of conversion is determined by repeatedly determining the non-volatile fraction of the reaction mixture (in a forced air oven for 15 minutes at 180 ° C.) and determining the viscosity .
- the resulting polymer solution has a non-volatile fraction (measured in a convection oven 60 mm. At 130 ° C.) of 60.2%.
- the polymer has an acid number of 21.6 mgKOH / g, an OH number of 120 mgKOH / g (both based on the non-volatile fraction) and a solution viscosity of 825 mPa * »s, measured on the solution described in an ICI -Plate-cone viscometer at 23 ° C.
- the paints of Examples 1 and 2 and of Comparative Example 1 are produced as follows from the components given in Table 1.
- the acrylic resin described above is included 1.) a mixture of the blocked polyisocyanate B1 and the blocked polyisocyanate B3 (example 1) or
- Dry film thickness of 14 ⁇ m results.
- the mixture is then flashed off at room temperature for 5 minutes and then the varnish of Examples 1 and 2 or of Comparative Example VI is applied in two spray passes in such a way that a dry film thickness of 40 ⁇ m results.
- the panel is flashed off at room temperature for 5 minutes and then baked at 130 ° C for 30 minutes.
- the solution from the mixture of the blocked polyisocyanate B1 and B3 and the solution of the blocked polyisocyanate B2 have been in use for more than 6 months Storage stable at room temperature.
- the solution of the blocked polyisocyanate B3 crystallizes after storage for a few days at room temperature.
- the LacKe with the mixture of blocked polyisocyanates Bl and B3 and the lacquer with blocked polyisocyanate B2 are stable for 3 weeks after storage at a temperature of 40 ° C and show only a slight increase in viscosity.
- the lacquer with the blocked polyisocyanate B3 is cloudy after 1 week of storage at a temperature of 40 ° C. and shows a greater increase in viscosity.
- the clearcoat films of Examples 1 and 2 are readily acid-resistant, show no noticeable yellowing over a silver basecoat and are scratch-resistant.
- the clearcoat film of Comparative Example 1 is less resistant to yellowing, less hard and less glossy.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19748584A DE19748584A1 (de) | 1997-11-04 | 1997-11-04 | Verfahren zur Herstellung einer mehrschichtigen Lackierung und für diese Verfahren geeignete Lacke |
DE19748584 | 1997-11-04 | ||
PCT/EP1998/006825 WO1999023133A1 (de) | 1997-11-04 | 1998-10-28 | Verfahren zur herstellung einer zweischichtigen lackierung und für dieses verfahren geeignete lacke |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1030871A1 true EP1030871A1 (de) | 2000-08-30 |
EP1030871B1 EP1030871B1 (de) | 2002-04-17 |
Family
ID=7847512
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98961107A Expired - Lifetime EP1030871B1 (de) | 1997-11-04 | 1998-10-28 | Verfahren zur herstellung einer zweischichtigen lackierung und für dieses verfahren geeignete lacke |
Country Status (9)
Country | Link |
---|---|
US (1) | US6274693B1 (de) |
EP (1) | EP1030871B1 (de) |
JP (1) | JP2001521956A (de) |
AR (1) | AR017766A1 (de) |
AU (1) | AU1664899A (de) |
BR (1) | BR9813909A (de) |
DE (2) | DE19748584A1 (de) |
ES (1) | ES2175830T3 (de) |
WO (1) | WO1999023133A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2905084A4 (de) * | 2012-10-01 | 2016-06-22 | Kansai Paint Co Ltd | Verfahren zur bildung eines mehrschichtigen beschichtungsfilms |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3884277B2 (ja) * | 2001-02-21 | 2007-02-21 | 関西ペイント株式会社 | ブロックイソシアネート基含有樹脂組成物及びこれを含む熱硬化性組成物 |
US6891012B2 (en) * | 2003-05-23 | 2005-05-10 | Bayer Materialscience Llc | Powder coatings produced with crosslinkers capable of curing at low temperatures and coated articles produced therefrom |
CA2487916A1 (en) * | 2003-12-04 | 2005-06-04 | Rohm And Haas Company | One-component flexible etch resistant clearcoat |
US20050123781A1 (en) * | 2003-12-04 | 2005-06-09 | Drescher James C. | One-component flexible etch resistant clearcoat |
US7371807B2 (en) * | 2004-10-21 | 2008-05-13 | Bayer Materialscience Llc | Blocked biuretized isocyanates |
US20060089481A1 (en) * | 2004-10-21 | 2006-04-27 | Roesler Richard R | Blocked biuretized isocyanates |
US20060089480A1 (en) * | 2004-10-21 | 2006-04-27 | Roesler Richard R | Biuretized isocyanates and blocked biuretized isocyanates |
JP2006335954A (ja) * | 2005-06-03 | 2006-12-14 | Sumika Bayer Urethane Kk | ブロックポリイソシアネート組成物および一液型コーティング組成物 |
DE102008063085A1 (de) * | 2008-12-24 | 2010-07-01 | Basf Coatings Ag | Lackzusammensetzung |
EP2695680B1 (de) * | 2011-04-08 | 2016-03-30 | Kansai Paint Co., Ltd | Verfahren zur bildung mehrerer geschichteter lackfilme und beschichteter gegenstand |
CN103492448B (zh) | 2011-04-08 | 2015-07-29 | 关西涂料株式会社 | 嵌段多异氰酸酯化合物 |
EP2818252B1 (de) * | 2012-02-24 | 2020-05-27 | Kansai Paint Co., Ltd. | Verfahren zur herstellung eines mehrschichtigen films und beschichteter artikel |
WO2013151050A1 (ja) * | 2012-04-03 | 2013-10-10 | 関西ペイント株式会社 | 水性塗料組成物及び塗膜形成方法 |
JP6073291B2 (ja) * | 2012-04-04 | 2017-02-01 | 関西ペイント株式会社 | 水性塗料組成物、及び塗装物品の製造方法 |
US9404010B2 (en) | 2012-09-20 | 2016-08-02 | Kansai Paint Co., Ltd. | Method for forming multilayer coating film |
JP2017095533A (ja) * | 2015-11-18 | 2017-06-01 | 旭化成株式会社 | ブロックポリイソシアネート組成物、熱硬化性組成物、及び硬化物 |
JP6713748B2 (ja) * | 2015-10-22 | 2020-06-24 | 旭化成株式会社 | ブロックポリイソシアネート組成物 |
JP6591241B2 (ja) * | 2015-09-11 | 2019-10-16 | 旭化成株式会社 | ブロックポリイソシアネート組成物、一液型コーティング組成物、塗膜、及び塗装物品 |
JP6849353B2 (ja) * | 2015-09-11 | 2021-03-24 | 旭化成株式会社 | ブロックポリイソシアネート組成物、一液型コーティング組成物、塗膜、及び塗装物品 |
WO2017043646A1 (ja) * | 2015-09-11 | 2017-03-16 | 旭化成株式会社 | ブロックポリイソシアネート組成物、一液型コーティング組成物、塗膜、及び塗装物品 |
CN111183167B (zh) * | 2017-09-28 | 2022-07-19 | 旭化成株式会社 | 封端多异氰酸酯组合物及其应用 |
EP3636687A1 (de) * | 2018-10-12 | 2020-04-15 | Evonik Operations GmbH | Thermisch lösbare reaktivklebstoffe |
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DE2639491B1 (de) * | 1976-09-02 | 1978-02-02 | Hoechst Ag | Einbrennlacke auf der Grundlage von freie Hydroxylgruppen enthaltenden Polyester- und/oder Alkydharzen und blockierten Polyisocyanaten |
US4727100A (en) | 1986-08-15 | 1988-02-23 | E. I. Du Pont De Nemours And Company | Coating composition containing a reactive urethane component an acrylic fatty acid drying oil resin and a metallic alkylate |
DE3734916A1 (de) * | 1987-10-15 | 1989-04-27 | Hoechst Ag | Haertungskomponente fuer kunstharze, diese enthaltende haertbare mischungen sowie deren verwendung |
DE3918510A1 (de) * | 1989-06-07 | 1990-12-13 | Basf Lacke & Farben | Verfahren zur herstellung von steinschlagbestaendigen beschichtungen |
DE4204518A1 (de) * | 1992-02-15 | 1993-08-19 | Basf Lacke & Farben | Verfahren zur herstellung einer zweischichtigen lackierung und fuer dieses verfahren geeignete nicht-waessrige lacke |
DE19519396A1 (de) | 1995-05-26 | 1996-11-28 | Huels Chemische Werke Ag | Neue blockierte Polyisocyanate sowie ein Verfahren zu ihrer Herstellung |
JP3712295B2 (ja) * | 1996-04-12 | 2005-11-02 | 旭化成ケミカルズ株式会社 | ブロックポリイソシアネート組成物及びそれを用いた一液性熱硬化組成物 |
-
1997
- 1997-11-04 DE DE19748584A patent/DE19748584A1/de not_active Ceased
-
1998
- 1998-10-28 AU AU16648/99A patent/AU1664899A/en not_active Abandoned
- 1998-10-28 DE DE59803881T patent/DE59803881D1/de not_active Expired - Fee Related
- 1998-10-28 EP EP98961107A patent/EP1030871B1/de not_active Expired - Lifetime
- 1998-10-28 WO PCT/EP1998/006825 patent/WO1999023133A1/de active IP Right Grant
- 1998-10-28 US US09/530,667 patent/US6274693B1/en not_active Expired - Fee Related
- 1998-10-28 BR BR9813909-6A patent/BR9813909A/pt not_active Application Discontinuation
- 1998-10-28 ES ES98961107T patent/ES2175830T3/es not_active Expired - Lifetime
- 1998-10-28 JP JP2000519002A patent/JP2001521956A/ja active Pending
- 1998-11-04 AR ARP980105553A patent/AR017766A1/es unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9923133A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2905084A4 (de) * | 2012-10-01 | 2016-06-22 | Kansai Paint Co Ltd | Verfahren zur bildung eines mehrschichtigen beschichtungsfilms |
Also Published As
Publication number | Publication date |
---|---|
DE19748584A1 (de) | 1999-05-06 |
DE59803881D1 (de) | 2002-05-23 |
JP2001521956A (ja) | 2001-11-13 |
AR017766A1 (es) | 2001-10-24 |
EP1030871B1 (de) | 2002-04-17 |
ES2175830T3 (es) | 2002-11-16 |
BR9813909A (pt) | 2000-09-26 |
US6274693B1 (en) | 2001-08-14 |
WO1999023133A1 (de) | 1999-05-14 |
AU1664899A (en) | 1999-05-24 |
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